The invention relates to curable compositions of glycidyl compounds and aminic curing agents, which comprise as curing accelerators dialkyldipropylenetriamines and/or reaction products thereof with formaldehyde and/or phenolic compounds.
Curable compositions based on glycidyl compounds and aminic curing agents are widely used in industry for coating and improving the quality of metallic and mineral surfaces.
As amines there are used especially aliphatic, cycloaliphatic, aromatic or araliphatic compounds and also optionally imidazolidine-group-containing polyaminoamides based on mono- or poly-basic acids and also adducts thereof with epoxy resins.
Such compounds are described in Lee and Neville, Handbook of Epoxy Resins, 1967, Chapter 6/1 to 10/19.
Although the curable compositions based on epoxy resins and those amine compounds generally have a sufficiently long pot life, their curing rate after application to the various substrates is too low for many areas of application.
Furthermore, the viscosity of many compounds, especially of the higher epoxy resin adducts and of the polyaminoamides or their adducts, is relatively high, especially in the range of low temperatures below 20xc2x0 C.
The curing rate can be accelerated by the addition of suitable curing accelerators.
For that purpose, in most cases there are used Mannich bases of tertiary amines, e.g. tris(dimethylaminomethyl)phenol (DMP30).
Those compounds have the disadvantage, however, that on account of their relatively high viscosity, which has little viscosity-reducing effect on the curing agent, they cannot be used in many applications.
The aim of the present invention was therefore to provide curing accelerators that, by virtue of their own low viscosity, have a strongly viscosity-reducing effect on the curing agent and thus on the curable composition, while physical and mechanical properties are to remain of a high standard.
It has been found, surprisingly, that the above problem can be solved in the case of curable compositions based on epoxy resins and customary amine hardeners that comprise as curing accelerators dialkyldipropylenetriamines and/or reaction products thereof with formaldehyde and/or in the form of Mannich bases.
The invention therefore relates to curable compositions comprising a) an epoxy resin, b) an aminic curing agent and c) a curing accelerator,
which comprise as curing accelerator c) at least one or more than one compound selected from
c1) a compound of formula (I) 
wherein R1 and R2 are each independently of the other a hydrocarbon radical having from 1 to 12 carbon atoms,
c2) a reaction product of a compound of formula (I) with formaldehyde, and
c3) a reaction product of a compound of formula (I) with formaldehyde and a phenolic compound,
in an amount of from 0.1 to 25% by weight, based on the sum of components a), b) and c).
The compounds of formula (I) are usually prepared by cyanoethylation of dialkylaminopropylamines in a molar ratio of dialkylaminopropylamine to acrylonitrile of 1:1 and subsequent hydrogenation in accordance with procedures known per se.
It is preferable to use amines in which the radicals R1 and R2 are each independently of the other a hydrocarbon radical having from 1 to 8 carbon atoms, preference being given to amines in which the radicals R1 and R2 are each independently of the other methyl, ethyl, propyl, isopropyl, butyl or isobutyl.
The reaction products of formaldehyde with amines of the general formula (I) 
wherein R1 and R2 are as defined above, which reaction products are used according to the invention in the curable mixtures, yield heterocyclic amines according to formula (II). It is preferable to use a molar ratio of formaldehyde to amine of from 1:1 to 3:2.
The invention therefore relates also to curable compositions comprising a) an epoxy resin, b) an aminic curing agent and c) a curing accelerator, which comprise as curing accelerator c2) a compound of formula (II) 
wherein R1 and R2 are each independently of the other a hydrocarbon radical having from 1 to 12 carbon atoms, R3 is a hydrogen atom when n=1 or R3 is methylene when n=2, obtainable by reaction of a compound of formula (I) with formaldehyde in a molar ratio of from 1:1 to 2:3.
Preparation is generally carried out by adding formaldehyde, preferably paraformaldehyde, in portions to the amine. The reaction proceeds exothermically. The addition of the formaldehyde is therefore controlled in such a manner that the reaction temperature does not exceed about 100xc2x0 C. According to the invention the operation is preferably carried out at about from 30xc2x0 C. to 80xc2x0 C. When all the formaldehyde has been added, the water of reaction formed is removed from the reaction mixture by increasing the temperature to about 130xc2x0 C,, optionally under reduced pressure. The residue that remains behind can be used as curing accelerator without further working-up.
The reaction products of formaldehyde and phenolic compounds with amines of the general formula (I) 
wherein R1 and R2 are as defined above, which reaction products are used according to the invention in the curable mixtures, are so-called Mannich bases.
Such Mannich bases are obtainable according to procedures known per se. The molar ratios depend upon the degree of substitution desired and the functionality of the phenolic component. For example, the molar ratio for phenol can be varied between 3:1 and 1:1, while the degree of substitution for ortho-cresol is between 2:1 and 1:1 and e.g. for 4,4xe2x80x2-di-hydroxydiphenylmethane is between 4:1 and 1:1. The molar ratio of amine per hydroxyl group of the phenolic compound is preferably from 3:1 to 1:1. The molar ratio of amine to formaldehyde is preferably from equimolar to a slight molar excess of formaldehyde.
The invention therefore relates also to curable compositions comprising a) an epoxy resin, b) an aminic curing agent and c) a curing accelerator, which comprise as curing accelerator c3) a compound obtainable by reaction of a compound of formula (I), formaldehyde and a phenolic compound, the molar ratio of amine per hydroxyl group of the phenolic compound being from 3:1 to 1:1 and of amine to formaldehyde being from 1:1 to 1.0:1.2.
As phenols it is possible to use, for example: monophenols, such as phenol, ortho-, meta- or para-cresol, the xylenol isomers, para-tertiary butylphenol, para-nonylphenol, naphthol and also di- and poly-phenols, such as resorcinol, hydroquinone, 4,4xe2x80x2-dihydroxydiphenyl, 4,4xe2x80x2-dihydroxydiphenyl ether, 4,4xe2x80x2-dihydroxydiphenylsulfone, 4,4xe2x80x2-dihydroxydiphenylmethane (bisphenol F), dihydroxydiphenylpropane (bisphenol A). Bisphenol A and bisphenol F are preferred. As aldehyde component there may be used any compound that yields formaldehyde under the given reaction conditions, e.g. trioxane or paraformaldehyde.
The curing accelerators c) according to the invention are used in the curable compositions in amounts of from 0.1 to 25% by weight, preferably from 1 to 10% by weight, based on the sum of components a), b) and c).
The epoxy compounds (a) used according to the invention are commercially available products having more than one epoxy group per molecule that are derived from mono- or/and poly-valent, mono- or/and poly-nuclear phenols, especially bisphenols, and also novolaks. A comprehensive list of such di- or poly-phenols can be found in the handbook xe2x80x9cEpoxidverbindungen and Epoxidharzexe2x80x9d by A. M. Paquin, Springer Verlag, Berlin, 1958, Chapter IV, and Lee and Neville xe2x80x9cHandbook of Epoxy Resinsxe2x80x9d, 1967, Chapter 2.
It is also possible to use mixtures of two or more of the epoxy resins. It is preferable to use glycidyl compounds based on bisphenol A (4,4xe2x80x2-dihydroxy-diphenylpropane-2,2) and/or bisphenol F (4,4xe2x80x2-dihydroxy-diphenylmethane) having epoxy values of from 0.4 to 0.62.
It is also possible to use mixtures of epoxy resins with so-called reactive diluents, e.g. monoglycidyl ethers of phenols or mono- or di-functional aliphatic or cycloaliphatic alcohols. Such reactive diluents are used primarily for reducing viscosity and, since they have an unfavourable effect on the final properties of the thermoset, should be used only in small amounts.
The epoxy resins mentioned by way of example can be used both for the curable combinations and for the preparation of the curing agent/epoxide adducts which can likewise be used in the process according to the invention.
The aminic curing agents (b) used according to the invention are aliphatic, cycloaliphatic, araliphatic or aromatic amines, optionally imidazoline-group-containing aminoamides, that preferably contain more than two reactive amine hydrogen atoms per molecule, and also adducts thereof with glycidyl compounds. Such compounds are part of the general prior art and are described, for example, in Lee and Neville, xe2x80x9cHandbook of Epoxy Resinsxe2x80x9d, Mc Graw Hill Book Company, 1967, Chapter 6-10.
For coating metallic or mineral substrates it is preferable to use cycloaliphatic amines or polyaminoamides based on mono- or poly-basic carboxylic acids and polyalkylenepolyamines and also adducts thereof with glycidyl compounds.
Those curing agents are commercially available products and are available, for example, from Ciba GmbH under the trade mark ARADUR(copyright), especially ARADUR (AD) 43, AD 46, AD 350.
The compounds of formula (I) can, on account of the number of reactive amine hydrogen atoms they contain, also be used as hardeners for epoxy resins. Curing agents and epoxy compounds are used in the process according to the invention preferably in approximately equivalent amounts, that is to say based on active amine hydrogen atoms and reactive epoxy groups. It is also possible, however, to use curing agent or glycidyl component in more than or less than the stoichiometric amount. The amounts in question lie in the range of about from 10 to 200% by weight, based on glycidyl compounds, and are governed by the final properties desired in the reaction product. Customary catalytic hardeners for epoxy resins can be used alongside the curing accelerators according to the invention.
The procedure is generally to add the curing accelerators according to the invention and the customary catalytic or reactive hardeners in the desired ratio to the epoxy compound separately or in the form of a mixture.
The mixing ratio of glycidyl compound to the curing accelerators c) used according to the invention is controlled in dependence upon the particular compound used and the final properties desired in the cured end products.
Generally, when liquid glycidyl ethers based on bisphenol A or bisphenol F having epoxy values of from about 0.40 to about 0.62 are used, the accelerator is used in an amount of from 0.1 to 25% by weight, based on the curable mixture; according to the invention an amount of about from 1 to 10% by weight is preferred.
The special advantage of the curable compositions according to the invention lies in their excellent curing behaviour at temperatures of from 10xc2x0 C. to 25xc2x0 C. and high relative humidity values of up to about 95%.
Depending upon the field of application and the intended use, there may be added to the compositions of epoxy resin, curing agent and accelerator according to the invention the auxilaries and additives customarily used for curable epoxy resin compositions in the form of inorganic and/or organic additives, such as finely particulate sands, talcum, silicic acid, argillaceous earth, metals or metal compounds in the form of chips or powders, thixotropic agents, fibrous materials, e.g. asbestos and glass staple fibres, pigments, flame retardants, solvents, dyes, plasticisers, bitumen and mineral oils.
The curable compositions according to the invention can be used in the coating of absorbent and non-absorbent substrates, for example natural stone, marble, concrete, metals, glass, and also as adhesives and sealants, and for the production of mouldings.
Analysis methods
Viscosity
Measured using a Haake rotary viscometer RV 20 in accordance with the manufacturer""s instructions.
Colour value
Measured in accordance with DIN 53 995 using the Lovibond colour-measuring apparatus (Hazen colour value, APHA).
Amine number
Measured in accordance with DIN 16 945.
Tecam value
Value for the gelation time, measured using a Tecam Gelation Timer GT3 from Techne, Cambridge, GB, at 23xc2x0 C. and 50% relative humidity. Sample mixture of resin and hardener and accelerator=250 g.
Shore D Hardness
Measured using Type 38009 apparatus from Karl Frank GmbH using test specimens 30 mm in diameter and 6 mm thick after 1, 2 and 3 days.